CN115116761B - Preparation method of high-capacity MXene composite fiber electrode material - Google Patents
Preparation method of high-capacity MXene composite fiber electrode material Download PDFInfo
- Publication number
- CN115116761B CN115116761B CN202210653284.9A CN202210653284A CN115116761B CN 115116761 B CN115116761 B CN 115116761B CN 202210653284 A CN202210653284 A CN 202210653284A CN 115116761 B CN115116761 B CN 115116761B
- Authority
- CN
- China
- Prior art keywords
- mxene
- fiber
- electrode material
- container
- mxene composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 125
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 239000007772 electrode material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 239000000017 hydrogel Substances 0.000 claims abstract description 38
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 19
- 238000007710 freezing Methods 0.000 claims abstract description 14
- 230000008014 freezing Effects 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 9
- 239000004815 dispersion polymer Substances 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 239000011521 glass Substances 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 229960005070 ascorbic acid Drugs 0.000 claims description 12
- 235000010323 ascorbic acid Nutrition 0.000 claims description 12
- 239000011668 ascorbic acid Substances 0.000 claims description 12
- 239000004964 aerogel Substances 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229920000767 polyaniline Polymers 0.000 claims description 8
- 229920000128 polypyrrole Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 229960002796 polystyrene sulfonate Drugs 0.000 claims description 2
- 239000011970 polystyrene sulfonate Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 238000001338 self-assembly Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 13
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000013305 flexible fiber Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
Abstract
A preparation method of a high-capacity MXene composite fiber electrode material belongs to the technical field of energy materials. Ti is mixed with 3 C 2 T x The MXene, the Graphene Oxide (GO) and the conductive polymer dispersion liquid are uniformly mixed and dispersed, hydrothermal self-assembly is carried out through a space confinement effect to obtain the MXene composite hydrogel fiber, and then the MXene composite fiber electrode material with a radial channel structure is prepared through a radial freezing technology. Adopts Ti 3 C 2 T x MXene is designed to radially freeze hydrogel fibers, and a radial channel structure is firstly constructed in a fiber-based electrode material, so that the contact area of the electrode material and electrolyte is increased, active substances of the electrode material are fully utilized, and a rapid channel is provided for the transmission of ions in the electrolyte. The MXene composite fiber has good electrochemical performance and can be used as an electrode material of a supercapacitor.
Description
Technical field:
the invention relates to a preparation technology of a supercapacitor electrode material, in particular to a preparation method of a high-capacity MXene composite fiber electrode material, and belongs to the technical field of energy materials.
Background
In recent years, rapid development of wearable electronics has prompted research into flexible energy storage devices. In the aspect of wearable electronic devices, the fiber-based super capacitor has the advantages of portability, flexibility, high flexibility, braiding and the like, and has good development prospect in the field of flexible energy storage devices. The key to the preparation of fiber-based supercapacitors is the preparation of flexible fiber electrode materials with high capacity.
MXene is used as an emerging high-conductivity two-dimensional nanomaterial, and has high conductivity and excellent electrochemical performance. However, at present, a few of MXene fiber electrode materials are mainly prepared by wet spinning, and because of the stacking of MXene sheets, the inside of the fiber is generally in a relatively compact structure, which is unfavorable for the sufficient contact between the MXene nano sheets and the electrolyte, prevents the transmission of ions in the electrolyte in the electrode material, and cannot fully exert the high capacity characteristic of the MXene fiber.
The Ti with radial channel structure is prepared by combining the hydrothermal assembly and the radial freezing 3 C 2 T x The MXene-based composite fiber provides a direct and rapid path for ion transmission, effectively increases the sufficient contact between ions in electrolyte and electrode material surface active substances, and increases the sites of electrochemical reaction. Specifically, a proper amount of Graphene Oxide (GO), a conductive polymer and a reducing agent ascorbic acid are added into the MXene dispersion liquid, the graphene oxide can serve as a skeleton of the fiber in the hydrothermal process, the MXene forming is assisted, the flexibility of the fiber is improved, and meanwhile, the ascorbic acid can partially reduce the graphene oxide into reduced graphene oxide, so that the conductivity of the reduced graphene oxide is improved. The conductive polymer can be used as a conductive adhesive to enhance the stability of the structure, and can be used as a one-dimensional conductive material to link the two-dimensional nano sheets to form a more perfect conductive network so as to improve the conductivity of the fiber. The MXene composite hydrogel fiber obtained through hydrothermal reduction and self-assembly is placed in a low-temperature annular cold source, ice crystals grow from the surface of the fiber to the center along a temperature gradient, and finally the MXene composite aerogel fiber with a radial channel structure in the section is obtained through a method of sacrificing an ice template. The radial channel structure in the electrode material is proposed for the first time, provides a rapid path for the transmission of electrolyte ions in the fiber electrode material, effectively improves the capacitance of the fiber, and has a scanning rate of 5mV s -1 When the mass specific capacity reaches 475 F.g -1 Meanwhile, the glass has excellent multiplying power performance, and the scanning speed is up to 1000mV s -1 When the mass specific capacity is still maintained at 366F g -1 . The patent provides a new strategy for designing the two-dimensional nano sheet assembled fiber electrode material, and has good application prospect in the aspect of flexible electrode materials of energy storage devices of wearable electronic equipment.
Disclosure of Invention
The porous fiber section two-dimensional sheet layer obtained by combining the hydrothermal assembly forming, the radial freezing technology and the sacrificial ice template method is arranged in a radial channel structure, so that the stacking of the two-dimensional nano sheets is restrained, and a rapid transmission path can be provided for ions in electrolyte. The method has universality and provides a method for improving the capacity of the fibrous supercapacitor electrode material based on the two-dimensional nanomaterial. The prepared electrode material has excellent electrochemical performance.
The aim of the invention can be achieved by the following technical scheme:
a preparation method of a high-capacity MXene composite fiber electrode material is characterized by comprising the following steps of:
ti is mixed with 3 C 2 T x MXene and GO are respectively prepared into dispersion liquid, ti is prepared 3 C 2 T x After the MXene dispersion liquid and the GO dispersion liquid are mixed, conductive polymer dispersion liquid is added, and precursor dispersion liquid is uniformly mixed through ultrasonic and stirring. Ti is prepared in a sealed micro-reactor through space confinement effect and hydrothermal self-assembly 3 C 2 T x MXene composite hydrogel fiber. Transferring hydrogel fiber into low-temperature annular cold source designed by us, growing ice crystal along temperature gradient from surface of fiber to axis, and freeze drying to obtain Ti with radial channel structure 3 C 2 T x MXene composite aerogel fibers. The radial channel structure in the fiber can provide a rapid path for the transmission of ions in the electrolyte, effectively increases the contact area between the electrode material and the electrolyte solution, and is beneficial to the improvement of electrochemical performance. The fibrous electrode material exhibits high mass specific capacity.
The MXene composite fiber electrode material and the preparation method thereof are characterized in that the preparation process comprises the following steps:
(1) Preparing precursor dispersion liquid:
preparation of Ti 3 C 2 T x MXene dispersion liquid and GO dispersion liquid, mixing the two dispersion liquids according to a certain proportion, dispersing uniformly, adding conductive polymer dispersionThe solution and the reducing agent ascorbic acid are fully stirred and sonicated;
(2) Self-assembled MXene composite hydrogel fiber by hydrothermal method:
filling the precursor dispersion into a syringe, injecting into a hollow glass capillary tube at constant speed, sealing two ends, performing hydrothermal reaction, and performing Ti 3 C 2 T x The MXene, the GO and the conductive polymer are self-assembled in the hydrothermal process, and meanwhile, the GO is partially reduced into reduced graphene oxide (rGO) by ascorbic acid to obtain the MXene composite hydrogel fiber;
(3) Preparing the MXene composite aerogel fiber with a radial channel structure by a radial freezing method: vertically placing the MXene composite hydrogel fiber into a cold source with temperature difference along the radial direction around the MXene composite hydrogel fiber, enabling ice crystals in the MXene composite hydrogel fiber to grow along the radial direction of the fiber, and then performing freeze drying to obtain the MXene composite aerogel fiber with a radial channel structure;
ti in step (1) 3 C 2 T x The concentration of the MXene dispersion liquid is 5-20 mg.mL -1 The concentration of the graphene dispersion liquid is 5-20 mg.mL -1 The concentration of the conductive polymer dispersion was 10mg mL -1 The method comprises the steps of carrying out a first treatment on the surface of the The conductive polymer is selected from poly 3, 4-ethylenedioxythiophene: polystyrene sulfonate (PEDOT: PSS), polyaniline (PANI), polypyrrole (PPy);
ti in step (2) 3 C 2 T x The volume ratio of the MXene dispersion liquid to the GO dispersion liquid is 10:0.5-5, ti 3 C 2 T x The volume ratio of the MXene dispersion liquid to the conductive polymer dispersion liquid is 10:0-5, and the conductive polymer is preferably not 0; the mass ratio of the reducing agent ascorbic acid to GO is 1:1.
the inner diameter of the glass capillary tube in the step (2) is 0.5-2 mm;
the hydrothermal reaction temperature in the step (2) is 60-95 ℃ and the time is 2-10 h;
designing a radial refrigerating device, as shown in figure 1, wherein the container 1 is a vertical cylindrical stainless steel container (the diameter of the container 1 is 2-10cm, preferably 2cm, in the embodiment, the diameter is 2 cm), n-hexane or ethyl acetate is contained in the container 1, a mixed solution containing ethanol and water is contained in the container 2, the container 1 is located at the central position of the container 2, liquid nitrogen is poured into the mixed solution of ethanol and water in the container 2 until the solution freezes, a constant low-temperature environment in the container 2 is maintained, a glass capillary tube with MXene composite hydrogel fibers inside is quickly and vertically placed in the container 1, and the glass capillary tube is kept in the container 1 for a period of time, so that ice crystals grow from the peripheral axial center of the fibers along a temperature gradient, and the Mne aerogel fibers with a radial channel structure are subjected to freeze drying.
The volume fraction of ethanol in the mixed solution of ethanol and water in the container 2 is 30-95%, liquid nitrogen is added into the mixed solution to enable the mixed solution to be completely solidified, a stable outer-layer low-temperature environment is formed, the radial temperature adjustment range of the annular cold source in the container 1 is minus 20 ℃ to minus 90 ℃, hydrogel fibers are vertically placed in the container 1 for 5-20 min, and ice crystals are along the radial direction of the fibers.
Meanwhile, as a control, the MXene composite hydrogel fiber prepared in the step (2) is directly freeze-dried to obtain the MXene composite aerogel fiber with a circumferentially layered stacking structure in the section.
The invention relates to 2 basic principles:
(1) Hydrothermal self-assembly of MXene, rGO and conductive polymers
By directing Ti to 3 C 2 T x Conductive polymer is added into MXene and GO dispersion liquid to increase electronegativity of the system, and Ti is realized through hydrothermal process 3 C 2 T x The method comprises the steps of (1) self-assembling an MXene nano-sheet, a GO nano-sheet and a conductive polymer to prepare hydrogel fibers;
(2) Principle of radial freezing
By applying annular cold source to the hydrogel fiber, the ice crystals grow from the edge of the fiber to the axis along the temperature gradient direction, namely along the diameter direction of the fiber, and the aerogel fiber with a radial channel structure is formed by a freeze drying sacrificial ice template method.
Description of the drawings:
FIG. 1 is a schematic view of a radial freezer;
FIG. 2 is an SEM scan image of a cross section of an aerogel fiber;
wherein a-b are the corresponding MXene/rGO/PEDOT with radial channel structure of example 1, PSS (D-MGP 1) fiber cross-sectional structure scan image, and c-D are the corresponding MXene/RGO/PEDOT with radial random structure of example 2, PSS (U-MGP 1) fiber cross-sectional structure scan image;
FIG. 3 is a graph showing the electrochemical test curves of D-MGP1 fiber in a three electrode test system, wherein a-b are cyclic voltammetry test curves of the material of example 1 at different scanning rates, and c-D are cross-current charge and discharge test curves of the material of example 1 at different current densities;
FIG. 4 is an electrochemical test curve of the corresponding U-MGP1 fiber without radial channel structure of example 2 in a three electrode test system, wherein a-b are cyclic voltammetry test curves at different scan rates, and c-d are cross-current charge and discharge test curves at different current densities.
Detailed Description
The invention is further illustrated by the following examples: the following parts are mass parts unless otherwise specified. Not specifically identified are composite fibers having a radial channel structure.
The three-electrode testing method for the mass specific capacity of the fiber comprises the following steps:
the MXene composite fiber with the length of 1cm is used as a working electrode, a silver chloride electrode is used as a reference electrode, a platinum sheet is used as a counter electrode to form a three-electrode system for electrochemical test, and 3M H is adopted 2 SO 4 The aqueous solution was used as electrolyte using the Shanghai Chen Hua CHI660 electrochemical workstation. Respectively performing cyclic voltammetry test (CV) and constant current charge discharge test (GCD), wherein the scanning rate in the cyclic voltammetry test is 5-1000 mV.s -1 The current density in the cross-flow charge and discharge test is 0.5-5 A.g -1 And calculating the mass specific capacity of the fiber according to the cyclic voltammetry test curve.
Example 1: MXene/rGO/PEDOT: PSS composite fiber
Step 1: preparation of MXene and GO dispersion. 15 parts of deionized water and 45 parts of concentrated hydrochloric acid are added into a polytetrafluoroethylene reaction kettle, the mixture is placed in an ice bath and stirred for 10min, and 4.8 parts of lithium fluoride (LiF) is added into the reaction kettle for reaction for 30min. Taking 3 partsTi 3 AlC 2 Powder, which is added to the above reaction solution a small number of times, is ensured to be 0 ℃ during the raw material addition process. And transferring the reaction kettle into a heat-collecting magnetic stirrer, and continuously stirring for 24 hours at 35 ℃ to finish etching Al atoms. After the reaction is finished, the centrifugal water of the product is cooled to be neutral, the product is dispersed in water, the product is subjected to ultrasonic treatment for 60 minutes in an ice bath with 100 percent power under the atmosphere of argon, and then the product is centrifuged for 1 hour at 3500rpm, and the supernatant is collected and further concentrated to obtain 10mg mL -1 Ti of (2) 3 C 2 T x An aqueous solution of MXene. 0.2 part of graphene oxide powder prepared by a Hummers method is dispersed in 20 parts of deionized water to prepare 10mg mL -1 GO dispersion of (c).
Step 2: and preparing the MXene composite hydrogel fiber through hydrothermal assembly. 10 parts of Ti 3 C 2 T x MXene Dispersion (10 mg mL) -1 ) And 1 part GO dispersion (10 mg mL) -1 ) Mix, add 1 part PEDOT PSS dispersion (10 mg mL -1 ) And reducing agent ascorbic acid (the same as GO in mass), and stirring for 20min to uniformly mix the dispersion liquid to obtain the precursor dispersion liquid. The mixed solution was injected into a glass capillary tube having an inner diameter of 0.9mm through a syringe, and both ends were sealed by an alcohol lamp. And (3) placing the glass capillary tube in a blast oven for hydrothermal reduction at 85 ℃ for 3 hours to obtain the MXene/rGO/PEDOT: PSS hydrogel fiber.
Step 3: radial freezing preparation of MXene composite fibers with radial channel structure. The radial freezing device is shown in figure 1, a container 1 filled with normal hexane is placed in a container 2 filled with ethanol water solution with the volume fraction of 78.3%, liquid nitrogen is added into the ethanol water solution until the ethanol water solution is completely solidified to form a cold source with the temperature of minus 50 ℃, and a normal hexane solidification bath with the temperature of minus 50 ℃ is arranged in a stainless steel container. The hydrogel fiber is taken out of the glass capillary tube and vertically placed in an n-hexane coagulating bath for 5min, and ice crystals rapidly grow from the outside of the fiber to the axis along the temperature gradient. And then obtaining the MXene/rGO/PEDOT: PSS fiber (D-MGP 1) with radial channel structure by freeze drying the sacrificial ice template method, wherein the cross-section SEM images of the fiber are shown as a and b in figure 2, the electrochemical performance test result of the fiber is shown as figure 3, and the fiber is scannedThe trace rate was 5mV s -1 When the mass specific capacity reaches 475 F.g -1 Meanwhile, the glass has excellent multiplying power performance, and the scanning speed is up to 1000mV s -1 When the mass specific capacity is still maintained at 366F g -1 。
EXAMPLE 2 (comparative) non-radial frozen MXene/rGO/PEDOT: PSS composite fiber
Step 1: the MXene and GO dispersions were prepared as in step 1 of example 1.
Step 2: MXene/rGO/PEDOT PSS hydrogel fibers were prepared as in example 1, step 2.
Step 3: and directly freeze-drying to prepare the MXene composite fiber. The MXene/rGO/PEDOT: PSS hydrogel fiber prepared in the step 2 is directly freeze-dried to obtain the MXene/rGO/PEDOT: PSS fiber (U-MGP 1) with a layered stacking structure in the section, the SEM images of the fiber sections are shown as c and d in figure 2, the electrochemical performance test result of the fiber is shown as figure 4, and the scanning speed is 5mV s -1 When the mass specific capacity is 397 F.g -1 。
Example 3MXene/rGO/PANI composite fiber
Step 1: the MXene and GO dispersions were prepared as in step 1 of example 1.
Step 2: and preparing the MXene composite hydrogel fiber through hydrothermal assembly. 10 parts of Ti 3 C 2 T x MXene dispersion and 2 parts GO dispersion were mixed and 4 parts PANI dispersion (10 mg mL -1 ) And reducing agent ascorbic acid (the same as GO in mass), and stirring for 20min to uniformly mix the dispersion liquid to obtain the precursor dispersion liquid. The mixed solution was injected into a glass capillary tube having an inner diameter of 1.5mm through a syringe, and both ends were sealed by an alcohol lamp. And (3) placing the glass capillary tube in a blast oven for hydrothermal reduction at 80 ℃ for 2 hours to obtain the MXene/rGO/PANI hydrogel fiber.
Step 3: radial freezing to prepare the MXene composite fiber with a radial channel structure. The radial freezing device is shown in figure 1, a container 1 filled with ethyl acetate is placed in a container 2 containing 36.1% ethanol water solution by volume fraction, liquid nitrogen is added into the ethanol water solution until solidification forms a cold source of-20deg.C, and ethyl acetate of-20deg.C is solidified in a stainless steel containerAnd (5) fixing the bath. Taking out the hydrogel fiber from the glass capillary, vertically placing in n-hexane coagulation bath for 10min, freeze drying to obtain MXene/rGO/PANI fiber with radial channel structure, testing electrochemical performance of the fiber, and scanning at a scanning rate of 5mV s -1 The mass specific capacity was 362 F.g -1 。
Example 4: MXene/rGO composite fiber
Step 1: preparation of MXene and GO dispersion. MXene was prepared in the same manner as in step 1 of example 1, taking 10 parts of Ti 3 C 2 T x MXene Dispersion (10 mg mL) -1 ) 10 parts of deionized water was added to give 5mg mL -1 Is a MXene dispersion of (C). 100mg of graphene oxide powder prepared by Hummers method is dispersed in 20mL of deionized water to prepare 5mg mL -1 GO dispersion of (c).
Step 2: and preparing the MXene composite hydrogel fiber through hydrothermal assembly. Taking 8 parts of Ti 3 C 2 T x MXene Dispersion (5 mg mL) -1 ) And 4 parts GO dispersion (5 mg mL) -1 ) Mixing, adding reducer ascorbic acid (same as GO in mass), and stirring for 20min to obtain precursor dispersion. The mixed solution was injected into a glass capillary tube having an inner diameter of 0.5mm through a syringe, and both ends were sealed by an alcohol lamp. And (3) placing the glass capillary tube in a blast oven for hydrothermal reduction at 95 ℃ for 10 hours to obtain the MXene/rGO hydrogel fiber.
Step 3: radial freezing to prepare the MXene composite fiber with a radial channel structure. The radial freezing device is shown in figure 1, a container 1 filled with ethyl acetate is placed in a container 2 filled with an ethanol water solution with the volume fraction of 63.3%, liquid nitrogen is added into the ethanol water solution until solidification forms a cold source of-41 ℃, and an ethyl acetate solidification bath of-40 ℃ is arranged in a stainless steel container. Taking out the hydrogel fiber from the glass capillary, vertically placing the hydrogel fiber in an ethyl acetate coagulation bath for 20min, and obtaining the MXene/rGO fiber with a radial channel structure by a freeze-drying sacrificial ice template method, wherein the electrochemical performance of the fiber is tested, and the scanning speed is 5mV s -1 The mass specific capacity was 285 F.g -1 。
Example 5: MXene/rGO/PPy composite fiber
Step 1: preparation of MXene and GO dispersion. MXene was prepared in the same manner as in step 1 of example 1, and the MXene aqueous solution was concentrated to 20mg mL -1 Is an aqueous solution of MXene. 0.4 part of graphene oxide powder prepared by a Hummers method is dispersed in 20 parts of deionized water to prepare 20mg mL -1 GO dispersion of (c).
Step 2: and preparing the MXene composite hydrogel fiber through hydrothermal assembly. 10 parts of MXene dispersion (20 mg mL) was taken -1 ) And 0.5 part GO dispersion (20 mg mL) -1 ) Mixing, adding reducing agent ascorbic acid (same as GO by mass), and adding 0.1 part of 10mg mL -1 And (3) sufficiently stirring the PPy dispersion for 20min to uniformly mix the dispersion to obtain a precursor dispersion. The mixed solution is injected into a glass capillary tube with the inner diameter of 2mm through a syringe, and both ends are sealed through alcohol lamps. And (3) placing the glass capillary tube in a blast oven for hydrothermal reduction at 60 ℃ for 7 hours to obtain the MXene/rGO/PPy hydrogel fiber.
Step 3: radial freezing to prepare the MXene composite fiber with a radial channel structure. The radial freezing device is shown in figure 1, a container 1 filled with normal hexane is placed in a container 2 filled with ethanol water solution with the volume fraction of 95%, liquid nitrogen is added into the ethanol water solution until solidification forms a cold source with the temperature of minus 90 ℃, and a normal hexane solidification bath with the temperature of minus 90 ℃ is arranged in a stainless steel container. Taking out the hydrogel fiber from the glass capillary, vertically placing the hydrogel fiber in an n-hexane coagulating bath for 20min, and obtaining the MXene/rGO/PPy fiber with a radial channel structure by a freeze-drying sacrificial ice template method, wherein the electrochemical performance of the fiber is tested, and the scanning speed is 5mV s -1 When the mass specific capacity was 423 F.g -1 。
Results of the implementation
For example 2, the cross-section of the fibers was a stacked random structure, which was detrimental to adequate impregnation of the electrolyte and rapid transport of ions in the electrolyte. For examples 1,3,4,5, the cross-section of the fiber was able to create a radial channel structure. In the electrochemical performance test, for examples 2,3,4,5, the scan rate was 5mV s -1 The mass specific capacity is 285F g -1 ～423F g -1 Between which are located. For example 1, at a scan rate of 5mV s -1 Lower the specific capacity to 475F g -1 At a scan rate of up to 1000mV s -1 When the mass specific capacity is maintained at 366F g -1 。
Claims (9)
1. The preparation method of the high-capacity MXene composite fiber electrode material is characterized by comprising the following steps of:
(1) Preparing precursor dispersion liquid:
preparation of Ti 3 C 2 T x The preparation method comprises the steps of (1) mixing an MXene dispersion liquid and a GO dispersion liquid according to a certain proportion, uniformly dispersing, adding a conductive polymer dispersion liquid and a reducing agent ascorbic acid, stirring and carrying out ultrasound;
(2) Self-assembled MXene composite hydrogel fiber by hydrothermal method:
filling the precursor dispersion into a syringe, injecting into a hollow glass capillary tube at constant speed, sealing two ends, performing hydrothermal reaction, and performing Ti 3 C 2 T x The MXene, the GO and the conductive polymer are self-assembled in the hydrothermal process, and meanwhile, the GO is partially reduced into reduced graphene oxide (rGO) by ascorbic acid to obtain the MXene composite hydrogel fiber;
(3) Preparing the MXene composite aerogel fiber with a radial channel structure by a radial freezing method: vertically placing the MXene composite hydrogel fiber into a cold source with temperature difference along the radial direction around the MXene composite hydrogel fiber, enabling ice crystals in the MXene composite hydrogel fiber to grow along the radial direction of the fiber, and then performing freeze drying to obtain the MXene composite aerogel fiber with a radial channel structure;
ti in step (1) 3 C 2 T x The concentration of the MXene dispersion liquid is 5-20 mg.mL -1 The concentration of GO dispersion liquid is 5-20 mg.mL -1 ；Ti 3 C 2 T x The volume ratio of the MXene dispersion liquid to the GO dispersion liquid is 10:0.5-5; the conductive polymer is selected from poly 3, 4-ethylenedioxythiophene: polystyrene sulfonate (PEDOT: PSS), polyaniline (PANI), polypyrrole (PPy).
2. A method according to claim 1A method for preparing a high-capacity MXene composite fiber electrode material is characterized in that the concentration of conductive polymer dispersion liquid in the step (1) is 10mg mL -1 ；Ti 3 C 2 T x The volume ratio of the MXene dispersion liquid to the conductive polymer dispersion liquid is 10:0-5, and the conductive polymer is not 0; the mass ratio of the reducing agent ascorbic acid to GO is 1:1.
3. the method for preparing a high capacity MXene composite fiber electrode material according to claim 1, wherein the inner diameter of the glass capillary tube in the step (2) is 0.5-2 mm.
4. The method for preparing a high-capacity MXene composite fiber electrode material according to claim 1, wherein the hydrothermal reaction temperature in the step (2) is 60-95 ℃ and the time is 2-10 h.
5. The method for preparing the high-capacity MXene composite fiber electrode material according to claim 1, wherein the radial refrigerating device is designed in the step (3), the container 1 is an upright cylindrical stainless steel container, n-hexane or ethyl acetate is contained in the container 1, a mixed solution containing ethanol and water is contained in the container 2, the container 1 is located at the central position of the container 2, liquid nitrogen is poured into the mixed solution containing ethanol and water in the container 2 until the solution freezes, a constant low-temperature environment in the container 2 is maintained, a glass capillary tube with MXene composite hydrogel fibers inside is quickly and vertically placed in the container 1, and the container 1 is maintained for a period of time, so that ice crystals in the glass capillary tube grow from the periphery of the fibers to the axis along a temperature gradient, and the MXene aerogel fibers with a radial channel structure are subjected to freeze drying.
6. The method for preparing a high-capacity MXene composite fiber electrode material according to claim 5, wherein the volume fraction of ethanol in the mixed solution of ethanol and water in the container 2 is 30-95%, liquid nitrogen is added into the mixed solution to enable the mixed solution to be completely solidified, a stable outer-layer low-temperature environment is formed, the radial temperature adjustment range of the annular cold source in the container 1 is minus 20 ℃ to minus 90 ℃, hydrogel fibers are vertically placed in the container 1 for 5-20 min, and ice crystals are arranged along the radial direction of the fibers.
7. A method for producing a high-capacity MXene composite fiber electrode material according to claim 5, wherein the diameter of the container 1 is 2-10cm.
8. A high capacity MXene composite fiber electrode material prepared according to the method of any one of claims 1-7.
9. Use of a high capacity MXene composite fiber electrode material prepared according to the method of any one of claims 1-7 in a supercapacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210653284.9A CN115116761B (en) | 2022-06-09 | 2022-06-09 | Preparation method of high-capacity MXene composite fiber electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210653284.9A CN115116761B (en) | 2022-06-09 | 2022-06-09 | Preparation method of high-capacity MXene composite fiber electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115116761A CN115116761A (en) | 2022-09-27 |
| CN115116761B true CN115116761B (en) | 2024-03-26 |
Family
ID=83325608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210653284.9A Active CN115116761B (en) | 2022-06-09 | 2022-06-09 | Preparation method of high-capacity MXene composite fiber electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115116761B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170106857A (en) * | 2016-03-14 | 2017-09-22 | 한국에너지기술연구원 | Preparing method of the 3D porous structured graphene/Mxene composite by ice-templating method and 3D porous structured graphene/Mxene composite by the same method |
| CN107633954A (en) * | 2016-07-19 | 2018-01-26 | 中国科学院上海硅酸盐研究所 | A kind of graphene/MXene combination electrode materials and its application |
| CN110085436A (en) * | 2019-04-21 | 2019-08-02 | 北京工业大学 | A kind of preparation method of graphene/Polyglycolic acid fibre composite fibre assembly |
| CN111799097A (en) * | 2020-07-10 | 2020-10-20 | 西北工业大学 | Preparation method of graphene/MXene composite fiber flexible electrode material based on solid electrolyte and braided super capacitor |
| CN112310417A (en) * | 2020-11-05 | 2021-02-02 | 中国科学院合肥物质科学研究院 | Preparation method, product and application of three-dimensional platinum/Mxene-reduced graphene oxide catalyst |
| CN113185193A (en) * | 2021-04-07 | 2021-07-30 | 东南大学 | MXene composite fiber reinforced graphene aerogel wave-absorbing material and preparation method thereof |
| CN113745012A (en) * | 2021-07-28 | 2021-12-03 | 西交利物浦大学 | Preparation method and application of MXene/rGO @ charcoal hydrogel composite material |
-
2022
- 2022-06-09 CN CN202210653284.9A patent/CN115116761B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170106857A (en) * | 2016-03-14 | 2017-09-22 | 한국에너지기술연구원 | Preparing method of the 3D porous structured graphene/Mxene composite by ice-templating method and 3D porous structured graphene/Mxene composite by the same method |
| CN107633954A (en) * | 2016-07-19 | 2018-01-26 | 中国科学院上海硅酸盐研究所 | A kind of graphene/MXene combination electrode materials and its application |
| CN110085436A (en) * | 2019-04-21 | 2019-08-02 | 北京工业大学 | A kind of preparation method of graphene/Polyglycolic acid fibre composite fibre assembly |
| CN111799097A (en) * | 2020-07-10 | 2020-10-20 | 西北工业大学 | Preparation method of graphene/MXene composite fiber flexible electrode material based on solid electrolyte and braided super capacitor |
| CN112310417A (en) * | 2020-11-05 | 2021-02-02 | 中国科学院合肥物质科学研究院 | Preparation method, product and application of three-dimensional platinum/Mxene-reduced graphene oxide catalyst |
| CN113185193A (en) * | 2021-04-07 | 2021-07-30 | 东南大学 | MXene composite fiber reinforced graphene aerogel wave-absorbing material and preparation method thereof |
| CN113745012A (en) * | 2021-07-28 | 2021-12-03 | 西交利物浦大学 | Preparation method and application of MXene/rGO @ charcoal hydrogel composite material |
Non-Patent Citations (1)
| Title |
|---|
| 《Superelastic and ultralight electrospun carbon nanofiber/MXene hybrid aerogels with anisotropic microchannels for pressure sensing and energy storage》;Liyuan Qin;Journal of Colloid and Interface Science;第589卷;264-274 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115116761A (en) | 2022-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | N-doped honeycomb-like porous carbon towards high-performance supercapacitor | |
| Gao et al. | Hierarchical porous carbon sheets derived from biomass containing an activation agent and in-built template for lithium ion batteries | |
| Yin et al. | 3-Dimensional hierarchical porous activated carbon derived from coconut fibers with high-rate performance for symmetric supercapacitors | |
| Chen et al. | Sulfur nanoparticles encapsulated in reduced graphene oxide nanotubes for flexible lithium-sulfur batteries | |
| Zhang et al. | Facile preparation of 3D hierarchical porous carbon from lignin for the anode material in lithium ion battery with high rate performance | |
| Sun et al. | Mesoporous carbon materials prepared from litchi shell as sulfur encapsulator for lithium-sulfur battery application | |
| Zhao et al. | Design and synthesis of three-dimensional hierarchical ordered porous carbons for supercapacitors | |
| CN109385254B (en) | Graphene elastic polymer phase-change composite material and preparation method thereof | |
| Zhang et al. | Functional porous carbon-based composite electrode materials for lithium secondary batteries | |
| CN107871617A (en) | Graphene metal organic frame composite and its preparation method and application | |
| CN112094625A (en) | Boron nitride nanotube aerogel/phase change heat conduction composite material and preparation method thereof | |
| CN108923026B (en) | Preparation method of nitrogen-rich material with hollow carbon spheres filled with porous carbon nanosheets | |
| CN114156093B (en) | N/O co-doped molybdenum sulfide@porous carbon composite electrode material and preparation method and application thereof | |
| Gao et al. | Sulfur double encapsulated in a porous hollow carbon aerogel with interconnected micropores for advanced lithium-sulfur batteries | |
| Liang et al. | Facilitation of lithium polysulfides adsorption by nitrogen doped carbon nanofibers with 3D interconnected pore structures for high-stable lithium-sulfur batteries | |
| Hu et al. | Rose-petals-derived hemispherical micropapillae carbon with cuticular folds for super potassium storage | |
| Deng et al. | A hierarchically combined reduced graphene oxide/Nickel oxide hybrid supercapacitor device demonstrating compliable flexibility and high energy density | |
| Wu et al. | Green and facile synthesis of porous carbon spheres from waste solution for high performance all-solid-state symmetric supercapacitors | |
| Hu et al. | A lightweight nitrogen/oxygen dual-doping carbon nanofiber interlayer with meso-/micropores for high-performance lithium-sulfur batteries | |
| CN110817871A (en) | Preparation method and application of nitrogen-doped graphene-based carbon aerogel microspheres | |
| CN113929964A (en) | Preparation method of 5G waveband aerogel and polymer interpenetrating wave-absorbing material | |
| Wei et al. | N/S co-doped interconnected porous carbon nanosheets as high-performance supercapacitor electrode materials | |
| CN109713302A (en) | Under a kind of ultralow temperature can big multiplying power charge and discharge lithium ion battery and preparation method thereof | |
| Lu et al. | 3D carbiyne nanospheres boosting excellent lithium and sodium storage performance | |
| CN115116761B (en) | Preparation method of high-capacity MXene composite fiber electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |